Detergent compositions containing a textile softener

ABSTRACT

This invention relates to a combination of surface-active compounds utilizable in neutral to alkaline textile washing baths which comprises (a) from 20 to 90 percent by weight of customary surface-active compounds utilizable in neutral to alkaline textile washing baths selected from the group consisting of anionic surface-active compounds, amphoteric surface-active compounds, non-ionic surface-active compounds and mixtures thereof and (b) from 80 to 10% by weight of a textile softener selected from the group consisting of (1) compounds of the formula WHEREIN R1 and R2 are alkyl having from six to 18 carbon atoms and X is a trivalent link selected from the group consisting of WHERE N REPRESENTS AN INTEGER FROM 0 TO 2, M REPRESENTS AN INTEGER FROM 1 TO 2 AND P REPRESENTS AN INTEGER FROM 2 TO 3, COMPOUNDS OF THE FORMULA WHEREIN R3 and R4 are members selected from the group consisting of alkyl having from one to 23 carbon atoms and cycloalkylalkyl having from seven to 23 carbon atoms and R5 is a member selected from the group consisting of hydrogen, alkyl having from one to 23 carbon atoms and cycloalkylalkyl having from seven to 23 carbon atoms, with the proviso that the total number of carbon atoms in R1, R2 and R3 is from six to 24 carbon atoms and (2) water soluble salts thereof. Textile washing agents and textile auxiliary washing agents containing the above combinations of surface-active compounds, with or without a content of enzymes are also part of the invention.

aten

Fries et al.

[54] DETERGENT COMPOSITIONS CONTAINING A TEXTILE SOFIENER [72]Inventors: Walter Fries, Erkrath-Unterbach; Markus Berg,Dusseldorf-Holthausen; Manfred Dohr, Dusseldorf-Holthausen; AlfredKlrstahler, Dusseldorf, all of Germany [73] Assignee: Henkel & Cie GmbH,Dusseldorf, Germany [22] Filed: Jan. 14, 1970 [21] Appl.No.: 2,722

Related U.S. Application Data [63] Continuation-impart of Ser. No.745,952, July 18,

1 l968,abandoned.

[30] Foreign Application Priority Data Jan. 16, 1969 Germany..... ...P19 01 936.4 July 19, 1967 Germany ..l-l 63320 April 5, 1968 Germany ..P17 67 142.0

[52] U.S. Cl ..252/8.75, 1l7/139.5 F, 252/8.6,

[5.1] Int. Cl. ..Clld 1/04,C11d l/83, D06m 13/20 [58] FieldofSearch..260/534R,410,413,4l7,419; 252/8.6, 8.75, 8.8, 108, 109, 110, 132, 137,367,

Branched Chain Fatty Acids and Sulfonated Derivatives by W. C. Ault etal., The Journal of the American Oil Chemists Society, Vol. 4, Mar.1965,Pages 233- 236.

An Introduction to Textile Finishing by J. T. Marsh, published byChapman & Hall LTD, London, 1948, pages 259-266 TS 1510.M3

[451 July 11, 1972 Primary Examiner- Leon D. Rosdol AssistantExaminer-Dennis L. Albrecht A rtorney-Hammond & Littell ABSTRACT Thisinvention relates to a combination of surface-active compoundsutilizable in neutral to alkaline textile washing baths which comprises(a) from 20 to 90 percent by weight of customary surface-activecompounds utilizable in neutral to alkaline textile washing bathsselected from the group consisting of anionic surface-active compounds,amphoteric surface-active compounds, non-ionic surface-active compoundsand mixtures thereof and (b) from 80 to 10% by weight of a textilesoftener selected from the group consisting of 1 compounds of theformula wherein R and R are alkyl having from six to 18 carbon atoms andX is a trivalent link selected from the group consisting of where nrepresents an integer from 0 to 2, m represents an integer from 1 to 2and p represents an integer from 2 to 3, compounds of the formulawherein R and R, are members selected from the group consisting of alkylhaving from one to 23 carbon atoms and cycloalkylalkyl having from sevento 23 carbon atoms and R is a member selected from the group consistingof hydrogen, alkyl having from one to 23 carbon atoms andcycloalkylalkyl having from seven to 23 carbon atoms, with the provisothat the total number of carbon atoms in R R and R is from six to 24carbon atoms and (2) water soluble salts thereof. Textile washing agentsand textile auxiliary washing agents containing the above combinationsof surface-active compounds, with or without a content of enzymes arealso part of the invention.

18 Claims, 3 Drawing Figures United States Patent Fries et al.

July 11, 1972 PATENTED L 11 I 2 3.676.338

FIG.2

INVENTORS Walter Fries Markus Berg n m 2 3 1: i "IF-115K ATTO RNEYSDETERGENT COMPOSITIONS CONTAINING A TEXTILE SOFTENER REFERENCE TO APRIOR APPLICATION This application is a continuation-in-part of thecopending U.S. Pat. application Ser. No. 745,952, filed July 18, 1968,now abandoned.

THE PRIOR ART After drying washed textiles, especially those of cottonor similar cellulose fibers, a distinct harshening of the handle is tobe noted especially when these textiles have been washed in drum washingmachines. This phenomenon is particularly unpleasant in the case oflaundered articles which come in contact with human skin during use,particularly underwear, bed linen and towels. In addition, considerablevalue is also attached to a pleasant handle in the case of otherlaundered articles such as, for example, table linen.

It is known that this undesired harshening of the handle can be avoidedduring laundering by adding cationic substances which contain at leasttwo high molecular weight fatty residues in the molecule to the lastrinsing bath. In practice, dialkyl-dimethyl-ammonium salts suspendiblein water have been utilized for this purpose. Since these cationictextile softeners give water-insoluble precipitates with anionicdetergent substances, they cannot be added to the washing agent itself.Even when they are added to the last rinsing bath, precipitates may beformed from the reaction of the cationic textile softeners with theresidues of anionic detergent substances which are still present in therinsing water or on the fibers of the washed textiles.

In the British Patent specification, No. 1,052,847 it was proposed toadd cationic textile softeners to washing compositions based on anionicsurface-active compounds. However, an improvement of the handle of thewashed articles cannot be obtained in this way. The reason for thisprobably lies in the formation of the above-mentioned water-solubleprecipitates.

No previously known textile softeners compatible with anionic detergentsubstances have been reported, particularly for inclusion in thecustomary textile washing agents.

OBJECTS OF THE INVENTION An object of the invention is the obtention oftextile softeners which are substantive and compatible with neutral toalkaline textile washing agents.

Another object of the invention is the obtention of a combination ofsurface-active compounds utilizable in neutral to alkaline textilewashing baths which comprises (a) from 20 to 90 percent by weight ofcustomary surface-active compounds utilizable in neutral to alkalinetextile washing baths selected from the group consisting of anionicsurface-active compounds, amphoteric surface-active compounds, non-ionicsurface-active compounds and mixtures thereof and (b) from 80 to 10percent by weight of a textile softener selected from the groupconsisting of 1) compounds of the formula atoms and X is a trivalentlink selected from the group consisting of where n represents an integerfrom 0 to 2, m represents an integer from 1 to 2 and p represents aninteger from 2 to 3, compounds of the formula wherein R and R aremembers selected from the group consisting of alkyl having from one to23 carbon atoms and cycloalkylalkyl having from seven to 23 carbon atomsand R is a member selected from the group consisting of hydrogen, alkylhaving from one to 23 carbons atoms and cycloalkyl-alkyl having fromseven to 23 carbon atoms, with the proviso that the total number ofcarbon atoms in R R and R is from six to 24 carbon atoms and (2) watersoluble salts thereof.

A further object of the invention is the obtention of neutral toalkaline textile washing agents and washing adjuvants which contain from5 to percent by weight of the above combination of surface-activecompounds and the remainder of the customary washing agent components.

A still further object of the invention is the obtention of the abovecombination of surface-active compounds together with a further contentof enzymes, particularly proteases, amylases, lipases and mixturesthereof.

A yet further object of the invention is the obtention of neutral toalkaline textile washing agents and washing adjuvants containing from 5to 80 percent by weight of the above combination of surface-activecompounds together with a further content of enzymes.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

In the drawings:

FIG. 1 is a representation of a curtain tape;

FIG. 2 is a cross-section of the head of a conventional tensile testingmachine; and

FIG. 3 is a representation of the curtain tape in said tensile testingmachine after elongation.

DESCRIPTION OF THE INVENTION This invention relates particularly to acombination of anionic and/or amphoteric and/or non-ionic surface-activecompounds useful in neutral to alkaline textile washing baths, includingan anionic surface-active textile softener. This combination ofsurface-active compounds is characterized in that it contains (a) 20 topercent by weight, preferably 75 to 35 percent by weight, of surfaceactive compounds of the abovementionecl types and (b) as textilesoftener, 80 to 10 percent, preferably 25 to 65 percent, by weight of(1) a carboxylic acid of the general formula or its water-soluble salts,wherein R, and R represents straight or branched chain alkyl radicals,which may be the same or different, containing six to 18, preferablyeight to 12 carbon atoms, while X represents one of the followingtrivalent links:

in which n represents the whole number 0 to 2, m represents the wholenumbers 1 or 2 and p represents'the whole numbers 2 or 3. The number ofcarbon atoms present in R and R may be the same or different. Ifdifferent, the larger of the two alkyl radicals preferably contains notmore than twice as many, and in particular not more than 1.5 times asmany,carbon atoms as the smaller of the two alkyl radicals. Preferably,the sum of the total number of carbon atoms in R and R should be between12 and 24, especially between 14 and 20. In addition to the carboxylicacids indicated above, small amounts of similarly constructed compoundsmay be present which contain in the residues R R and perhaps also in theresidue X, more or less carbon atoms than the number indicated, withoutthe desired effect being thereby harmed, and (2) a carboxylic acid ofthe general formula Rs Ilia CCO01 or its water-soluble salts, wherein Rand R, represent aliphatic and/or cycloaliphatic residues, such as alkyland cycloalkylalkyl, preferably alkyl residues with one to 23,preferably one to 21 and in particular one to 19 carbon atoms and Rrepresents hydrogen or R The total number of carbon atoms in R R and Ris from six to 24 carbon atoms, preferably from seven to 19 carbonatoms.

The invention further relates to washing agents and washing agentadjuvants containing such combinations of surface-active compounds witha content of other customary washing agent constituents, in which casethe said combinations of sur' face-active compounds may constitute 5 to80 percent, preferably to 40 percent, by weight and the usual washingagent constituents may constitute to 95 percent, preferably 85 to 60percent by weight. Examples of the other customary washing agentconstituents are neutral to alkaline reacting builders, complex-formingcompounds, bleaching components, foam stabilizers, foam inhibitors anddirt carriers. Sufficient alkali is preferably present in the basicwashing composition substance for a 1 percent solution of the finishedwashing composition or washing assistant to have pH value in the regionof 8 to 12, preferably of9 to 11.

If the products according to the invention contain more than 45 percentby weight of the above combination of surface-active compounds, they aremostly not used as domestic washing agents, but are chiefly used inindustrial laundries and in the textile industry, where they are seldomused alone but" more often in combination with the usual additives. Insuch products, by-products from the preparation of the surface-activecompounds or the textile softeners may be present as well as the usualadditives.

Finally, the invention relates to combinations of surface-activecompounds and washing agents or washing agent adjuvants containingthese, which also contain enzymes.

Suitable enzymes are chiefly proteases, amylases and lipases, which maybe incorporated in the products according to the invention either aloneor in conjunction with one another. Where finished washing agents orwashing agent adjuvants are concerned, their protease content maycorrespond to activities of 50 to 5,000, preferably 100 to 2,500 LVE;their amylase content, to activities of 20 to 5,000, preferably 50 to2,000 SKBE; and their lipase content, to activities of 2 to 1,000,preferably 5 to 500 Le. per gram of said washing agent or washing agentadjuvant.

When the preparations according to the invention relate to combinationsof surface-active compounds which are frequently used in combinationwith the usual builders and additives in industrial laundries, theenzyme content of these preparations can be so high that the productcomposed of the respective combination of surface-active compounds usedand the other constituents of washing agent and washing agent adjuvantsimultaneously used has the above given enzyme content. Since thecombination of surface-active compounds may constitute 5 to 80 percent,preferably 15 to 40percent, of a finished washing agent or washing agentadjuvant, enzyme activities are calculated for the combinations ofsurface-active compounds which correspond to 62.5 to 100,000 LVE in thecase of proteases, to 100,000 SKBE in the case of amylases and 2.5 to20,000 [E in the case of lipases, per gram of the combinations ofsurface-active compounds. Of course, combinations of surface-activecompounds with such high enzyme activities as are present in the upperlimits, can only be prepared when very active enzyme preparations areavailable. Therefore, one is usually restricted to maximum values foractivity of 50,000 LVE, 50,000 SKBE and 10,000 113 per gram ofcombinations of surface-active compounds. The enzyme activities arepreferably in the range of 250 to 15,000 LVE, 125 to 15,000 SKBE, and12.5 to 3,500 1E per gram of combinations of surface-active compounds.

The above data on the content of enzymes and activities of thepreparations according to the invention are obtained from the activitiesof those enzyme preparations which are available at the present time,from the standpoint of economy, for use in the washing agent field. Fromthe technical-chemical standpoint the enzyme activities of thepreparations according to the invention can be increased, if feasible,so that the activities as regards proteases and amylases can be raisedto 5 times, and as regards lipases, to 10 times the above given maximumvalues. Therefore, should, in the future, enzyme preparations withhigher enzyme contents be supplied, which also appear suitableeconomically for use in washing agents, one has the choice either ofkeeping the enzyme activity of the preparation to the above given heightby use of smaller amounts of enzymes or of increasing the enzymeactivity with use of the same amount of enzymes.

The following references in the literature are referred to relative tothe determination of the enzyme activities:

Determination of the activity of proteases by Lohlein-Volhard:

A. Kunzel: Gerbereichemisches Taschenbuch, 6th Ed. Dresden and Leipzig,1955.

Determination of the activity of amylases:

J Wohlgemuth: Biochemische Zeitschrift," 1908, Vol. 9, pages 1 9; and

R. M. Sandsteadt, E. Kneen and M. J. Blish: Cereal Chemistry," 1939,Vol. 16, pages 712-723.

Determination of the activity of lipases:

R. Willstatter, E. Waldschmidt-Leitz and Fr. Memmen: Hoppe-SeylersZeitschrift fur physiologische Chemie," 1923, Vol. l25,pages 1l0l 17;and

R. Boissonas: Helvetia Chimica Acta, 1948, Vol. 31, pages 15714576.

The textile softeners of the formula wherein R,, R, and X have the abovevalues are readily available materials.

The nitrogen-free banched-chain carboxylic acids obtainable by knownprocesses, for example, by malonic ester synthesis or by catalyticaddition of olefins to carboxylic acids.

The Guerbet synthesis offers a further possible preparation. By thisprocess, aliphatic alcohols, especially those with six or more carbonatoms, are heated in the presence of finely divided alkali metalhydroxide, then a condensation takes place with formation of abranched-chain alcohol, water being split off between the hydroxyl groupof one alcohol molecule and a hydrogen atom on carbon atom 2 of a secondalcohol molecule. This branched-chain alcohol can then be oxidized ordehydrogenated to give the corresponding carboxylic acid.

Similarly constructed aminocarboxylic acids or their salts can beprepared from the corresponding dialkylamines, for example, by reactionwith methyl acrylate or chloroacetic acid esters and saponification ofthe product of addition, or by addition of chloracetic acid or itssalts. The compounds with carbonamide groups are obtained in a similarway from the corresponding dialkylamines by reaction with dicarboxylicacid anhydrides or by reaction with half ester chlorides of dicarboxylicacids and saponification of the ester group.

The textile softeners of the formula wherein R R and R have the abovevalues are likewise readily available materials.

Such carboxylic acids are commercially available in a simple way beaddition of carbon monoxide and water to olefins by the Koch process(see H. Koch: Brennstoff-chemie" (Fuel chemistry), 1955, vol. 26, pages321-328). There are a number of variants of this synthesis: referencemay be made to the publications, R.F. Goldstein and A. W. Waddams: ThePetroleum Chemicals Industry," London 1967, pages 207-209 and J. Falbe:Syntheses with carbon monoxide," Berlin and Heidelberg, 1967, pages120-128.

The synthesis does not consist only of an addition of carbon monoxideand water to the starting olefins; isomen'zations also take place, sothat the reaction products obtained represent a mixture of a variety ofisomers, in which the residues R to R may be approximately the same withrespect to their degree of branching and the number of carbon atomscontained therein, but may also be very different from one another. Suchisomeric mixtures are obtained in particular from mixtures of aliphaticolefms with terminal or non-terminal double bonds, which differ from oneanother with regard to the carbon number and/or the position of thedouble bond in the molecule. In a similar way, cycloaliphatic olefms orcycloaliphatic-aliphatic olefins or mixtures thereof with purelyaliphatic olefins can be converted into carboxylic acids of theabove-indicated structure.

Among suitable carboxylic acids under the above formula are those soldunder the trademark Versatic' acids. Theses acids are saturatedsynthetic tertiary monocarboxylic acids. Versatic" 911 acid contains amixture of acids having C C and C chain lengths. Versatic" 1519 acidcontins a mixture of acids having C, to C chain lengths and Versatic1621 acid contains a mixture of acids having C to C chain lengths.

The invention is not restricted; however, to the carboxylic acids ortheir water-soluble salts prepared by the said process, according to theinvention, carboxylic acids of the above given structure are alsoutilizable when they have been prepared by different processes. 7

All these compounds are denoted below, for the sake of simplicity, asbranched-chain carboxylic acids.

The above-described water-soluble salts of branched chain carboxylicacids serving as textile softeners in the composition according to theinvention are surface-active compounds and resemble soap in theirbehavior. This applies especially to alterations in the foaming power ofsynthetic, especially anionic, surface-active compounds. Thus, salts ofsuch branched chain carboxylic acids containing 20 and more carbon atomsin the molecule can reduce the foaming power of anionic surface-activecompounds. Therefore, other surface-active or non-surface-active foaminhibitors may be used in correspondingly smaller amounts or becompletely omitted.

The invention is of special practical importance for the socalledheavy-duty washing agents, that is for washing agents which are used inthe main washing operation. Machine washing agents with foam-inhibitingproperties are included thereby, but also all purpose washing agents,which show good foaming capacity at temperatures up to 60 C, while thedevelopment of foam abates more and more with the rise in temperatureabove 60 C. The surface-active components of such washing agents maysimultaneously contain foam stabilizers and foam inhibitors with anaction dependent on temperature.

Such surface-active components consist mostly of synthetic, anionic,amphoteric and/or non-ionic surface-active compounds as well as soapswith, for example, 12 to 18 carbon atoms in the fatty acid residue, orthe soaps of corresponding free fatty acids. The soap fraction may bewholly or partly replaced by the branchedehain carboxylic acids" usedaccording to the invention. The surface-active sulfonates, and also thecorresponding sulfates have special practical importance as thesynthetic anionic surface-active compounds. The anionic surface-activecomponent usually constitutes at least 50 percent of all the types ofsynthetic surface-active compounds mentioned under (a) in thecombination of surface-active compounds.

The foaming capacity of anionic and/or non-ionic surfaceactive compoundscan be affected by choice of suitable fatty acid components. Inhibitionof foaming, especially at temperatures from 60 to 5 C, increases withthe number of carbon atoms and the degree of saturation of the fattyacid residue. A considerable anti-foaming effect can be attained in thecase of synthetic anionic, amphoteric or non-ionic surfaceactivecompounds by inclusion therein of soaps from fatty acid mixtures whichcontain at least 50 percent of fatty acids with 16 to 30 carbon atomsand at least 3, preferably more than 5 percent, of fatty acids with 20or more carbon atoms. The saturated fatty acids containing at least 16carbon atoms preferably constituting at least 50 percent of the totalsoap fraction. This soap fraction in the combination of surface-activecompounds can be abolished, or replaced by synthetic detergentsubstances, provided the washing agent contains other foam-inhibitingsubstances, for example, those further defined under the said foaminhibitors.

When the heavy-duty washing agents according to the invention contain,in addition to the combinations of surface-active compounds, neutral toalkaline reacting builders, the amount of these usually lies in theregion of 0.5 to 7 times, especially 1 to 5 times, the amount of thecombination of surface-active compounds. Preferably alkalis are presentin the builders in such amount that a 1 percent solution of the finishedwashing agent has a pH value in the region of 8 to 12, preferably 9 to 11.

In practice, the composition of particularly valuable heavy duty washingagents generally lies within the range of the following formulation:

5 to percent, preferably 12 to 40 percent, by weight of combinations ofsurface-active compounds, consisting of 0 to 80 percent, preferably 25to 65 percent, by weight of synthetic surface-active compounds of thesulfonate and/or sulfate type,

0 to 80 percent, preferably 5 to 40 percent, by weight on non-ionicsurface-active compounds, 0 to 80 percent, preferably 10 to 50 percent,be weight of soap,

10 to 80 percent, preferably 25 to 65 percent, by weight of thebranched-chain carboxylic acids,

0 to 6 percent, preferably 0.5 to 3 percent, by weight of foamstabilizer,

0 to 8 percent, preferably 0.5 to 5 percent, by weight of foaminhibitor, preferably not a surface-active compound,

20 to 95 percent, preferably 60 to percent, by weight of builders, atleast a part of this'having an alkaline reaction and the quantity ofalkaline and neutral reacting builders preferably constituting 0.5 to 7times and especially 1 to 5 times, the amount of the total detergentsubstances,

35 to 30 percent by weight of other washing agent constituents, such as,for example, bleaching components and water.

The anionic, amphoteric or non-ionic surface-active compounds present inthe combinations of surface-active compounds or the washing agentscontaining them, according to the invention, contain in the molecule atleast one hydrophobic radical having eight to 30 carbon atoms, and ananionic or non-ionic water-solubilizing group. The hydrophobic radicalmay be of aliphatic or alicyclic, saturated or unsaturated nature and becombined with the water-solubilizing group directly or throughintermediate members. Suitable intermediate members are, for example,benzene rings, carboxylic acid ester or carboxylic acid amide groups,and ethylene glycol or propylene glycol residues.

The hydrophobic radical is preferably an aliphatic hydrocarbon radicalwith 10 to 18 carbon atoms, but deviations from this preferred range ofnumber of carbon atoms are possible, according to the nature of thesurface-active compound in question.

Soaps, which are derived from natural or synthetic fatty acids, possiblyfrom resin or naphthenic acids, are utilizable as the anionic detergentsubstances, especially when these acids have iodine values of not morethan 30 and preferably less than 10.

Among the synthetic anionic surface-active compounds, the sulfonates andsulfates possess particular practical importance.

The sulfonates includes, for example, the alkyl-aryl-sulfonates,especially the alkylbenZene-sulfonates, which among others, are obtainedfrom preferably straight chain, aliphatic hydrocarbons having 9 to 15,preferably to 14, carbon atoms, by chlorination and condensation withbenzene or from corresponding olefins with terminal or nonterminaldouble bonds by condensation with benzene, and sulfonation of thealkylbenzenes obtained. Furthermore, aliphatic sulfonates are ofinterest such as are obtainable, for example, from preferably saturatedhydrocarbons containing eight to 18 and preferably 10 to 16, carbonatoms in the molecule by sulfochlorination with sulfur dioxide andchlorine or sulfoxidation with sulfur dioxide and oxygen andconversation of the products thereby obtained into the sulfonates.Mixtures of alkene sulfonates, hydroxyalkene sulfonates andhydroxyalkane sulfonates are also useful as aliphatic sulfonates, suchas are obtained, for example, from C to C olefins with terminal ornon-terminal double bonds by sulfonation with sulfur dioxide, and acidor alkafine hydrolysis of the sulfonation products. In the aliphaticsulfonates thus prepared, the sulfonate group is frequently attached toa secondary carbon atom. However, sulfonates with a primary, i.e.,terminal, sulfonate group can also be prepared by reacting terminalolefins with a bisulfite.

The sulfonates to be used according to the invention also include estersof a-sulfo-fatty acids with monoor polyhydric alcohols containing one tofour and preferably one to two, carbon atoms.

Surface-active compounds of the sulfate type include fatty alcoholsulfates, especially those derived from coconut fatty alcohols, tallowfatty alcohols or from oleyl alcohol. Sulfonation products of thesulfate type utilizable according to the invention can also be preparedfrom C to C-olefins with terminal or non-terminal double bonds. Inaddition, belonging to this group of surface-active compounds aresulfated fatty acid alkylolamides, sulfated monoglycerides and sulfatedproducts of ethoxylated and/or propoxylated compounds such as fattyalcohols, alkylphenols with 8 to carbon atoms in the alkyl residue,fatty acid amides, fatty acid alkylolamides and so forth, where 0.5 to20, preferably 1 to 8, and advantageously 2 to 4 mol of ethylene and/orpropylene oxide are added to one mol of said compounds to be ethoxylatedand/or propoxylated.

Further useful sulfonates are the fatty acid esters ofhydroxyethanesulfonic acid and dihydroxypropanesulfonic acid, and thefatty acid amides of aminoethanesulfonic acid. The washing agentsaccording to the invention may also contain surface-active syntheticcarboxylates, for example, the fatty acid esters or fatty alcohol ethersof hydroxy-carboxylic acids as well as the fatty acid amides ofamino-carboxylic acids, for example, ofglycocoll or sarcosine,

Products which owe their solubility in water to the presence ofpolyether chains, amineoxide, sulfoxide or phosphineoxide groups,alkylolamide groups, and very generally to a number of hydroxyl groups,belong to the non-ionic surface-active compounds, denoted here asNon-ionics for the sake of simplicity.

The products obtainable by addition of ethylene oxide and/or glycide tofatty alcohols, alklyphenols, fatty acids, fatty amines, fatty acidamides and sulfonic acid amides are of special practical interest. TheseNon-ionics" may contain, per molecule, 4 to 100, preferably 6 to 40 andespecially 8 to 20, ether residues above all ethylene glycol etherresidues. Moreover, propylene or butylene glycol ether residues may bepresent either in these polyglycol ether residues or at their ends.

In addition, the Non-ionics" include the water-insoluble polypropyleneglycols made water-soluble by addition of ethylene oxide and known bythe trade-name of Pluronics," Tetronics or Ucon Fluid." Also additionproducts of propylene oxide to alkylenediamines or lower aliphaticalcohols containing one to eight and preferably three to six, carbonatoms are included as Non-ionics.

Further useful Non-ionics are fatty acid or sulfonic acid alkylolamides,which are derived, for example, from monoor dialkylolamines,dihydroxypropylamine or other polyhydroxyalkylamines, for example, theglycamines. They can be replaced by amides of higher primary orsecondary alkylamines and polyhydroxycarboxylic acids.

From the group of amineoxides, the Non-ionics derived from highertertiary amines having a hydrophobic alkyl residue and two shorter alkyland/or alkylol residues containing up to 4 carbon atoms each are ofparticular interest.

Amphoteric surface-active compounds contain in the molecule both acidand basic hydrophilic groups. To the acid groups belong carboxylic acid,sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoricacid partial ester groups. The basic groups may be primary, secondary,tertiary and quaternary ammonium groups.

Owing to their good compatibility with other surface-active compounds,carboxy, sulfate and sulfonate betaines have special practical interest.Suitable sulfobetaines are obtained, for example, by reacting tertiaryamines containing at last one hydrophobic alkyl residue with sultones,for example propaneor butanesultone. Corresponding carboxybetaines areobtained by reacting the said tertiary amines with chloroacetic acid,its salts or with chloroacetic acid esters and fission of the esterlinkage.

The foaming capacity of the washing agents according to the inventionmay be increased or reduced by suitable combinations of differentsurface-active compounds.

Suitable foam stabilizers in the case of surface-active compounds of thesulfonate or sulfate type, are chiefly surface-active carboxyorsulfo-betaines and also the abovementioned non-ionics of thealkylolamide type. Moreover, fatty alcohols or higher terminal diols areutilizable for this purpose.

Products with a reduced foaming capacity are chiefly intended for use inwashing and dish-washing machines, in which in some cases a limitedinhibition of foam is sufficient, while in other cases a strongeranti-foaming effect may be desired. Products which still foam in theaverage range of temperature up to about 65 C, but develop less and lessfoam as higher temperatures (70 C) are reached, are of particularpractical importance.

A reduced foaming power is often obtained with combinations ofdifferenttypes of surface-active compound, especially with combinations ofsynthetic anionic surface-active compounds, above all of (l) sulfatesand/or sulfonates or of (2) non-ionics on the one hand and (3) soaps onthe other hand. With combinations of components (1) and (2) or (1), (2)and (3), the foaming behavior can be influenced by the respective soapused. In the case of soaps from preferably saturated fatty acids with 12to 18 carbon atoms, the inhibition of foam is small, while a strongeranti-foaming effect is attained, especially in the higher temperaturerange, by soaps from saturated fatty acid mixtures with 20 to 26,preferably 20 to 22 carbon atoms, the amount of which may constitute 5to 10 percent by weight of the total soap fraction present in thesurface-active combination.

Among others, the addition products of propylene oxide to theabove-described non-ionic polyethylene glycol ethers are marked by asmall foaming capacity. By varying the number of ethylene glycol andpropylene glycol residues present in the molecule, products with a largevariety of turbidity points can be obtained. These Non-ionics act onother non-ionics as foam inhibitors at temperatures above theirturbidity point. They can, therefore, be used in the combinations ofsurfaceactive compounds according to the invention together with otherNon-ionics, and also in combination with other surface-active compounds,as for example, as the non-ionicconstituent in the alreadymentionedcombinations with sulfates and/or sulfonates, soapsand"Non-ionics."

The foaming capacity of the surface-active compounds, however, can alsobe reduced by additions of known, non-surface-active foam inhibitors.These include possibly chlorinecontaining N-alkylated aminotriazines,which are obtained by reacting 1 mol of cyanuric acid chloride with 2'to 3 mol of a monoand/or di-alkylamine with 6 to 20, preferably eight to18 carbon atoms in the alkyl residue. Aminotriazineormelamine-derivatives, which contain polypropylene glycol or polybutyleneglycol chains, while to 100 of such glycol residues may be contained inthe molecule, have a similar action. Such compounds are obtained, forexample, by addition of corresponding amounts of propylene and/orbutylene oxide to amin'otriazines, especially to melamine. Productspreferably used are obtained, for example, by reacting 1 mol of melaminewith at least 20 mol of propylene oxide or at least 10 mol of butyleneoxide. Products have been found to be speciallyactive which are obtainedby addition of 5 to 10 mol of propylene oxide to l molof melamine andfurther addition of 10 to 50 mol of butylene oxide to this propyleneoxide derivative.

The trito hexaalkylmelamines or dito tetra-alkyldiaminochlorotriazinesso obtained have a remarkably broad active spectrum independent of thenature of the surface-active compound in question.

Other non-surface-active, water-insoluble, organic compounds, such asparaffins or haloparaffins with melting points below 100 C, aliphatic Cto C -ketones and aliphatic carboxylic acids, which contain at least 18carbon atoms in the acid or in the alcohol residue, possibly also inboth of these two residues (for example triglycerides or fattyacid-fatty alcohol esters), can also be used as foam inhibitors,especially in combination with anionic synthetic surface-activecompounds and soaps.

The non-surface-active foam inhibitors are often only fully active attemperatures at which they are present in the liquid state, so that thefoaming behavior of the products can be controlled by choice of suitablefoam inhibitors in a similar way to the choice of soaps from fatty acidsof suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upontemperature, readily foaming products are obtained at lower temperatureswhile progressively more weakly foaming products are obtained as thetemperature approaches the boiling temperature.

Particularly weakly foaming non-ionics, which may be used both alone andin combination with anionic, amphoteric and non-ionic surface-activecompounds and reduce the foaming power of more strongly foaming,especially non-ionic, surfaceactive compounds, are addition products ofpropylene oxide to the above-described surface-active polyethyleneglycol ethers.

The combinations of surface-active compounds according to the inventionmay be put on the market as such, in order to combine them with washingalkalis, complex-forming compounds or other customary constituents ofwashing liquors, as is done, for example, in industrial laundries. Thecombinations of surface-active compounds, however, can also be processedtogether with these customary washing agent additives to a finishedwashing agent adjuvant.

Complete washing compositions usually also contain a bleachingcomponent. The bleaching component inclusive of stabilizers and/oractivators present, may constitute 2 to percent, preferably 7 to 30percent by weight of the total washing composition.

The complete washing compositions contain builders and inorganic saltsas well as inorganic and organic complex-forming compounds.

Salts which are weakly acid, neutral or alkaline reacting are utilizablein the compositions of the invention, for example, the alkali metalbicarbonates, carbonates, silicates, orthophosphates, sulfates and thealkali metal salts of organic,

non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylicacids containing one to eight carbon atoms. To the latter belong, forexample, water soluble salts of benzene-, toleueneor xylene-sulfonicacids, water-soluble salts of sulfoacetic acid, sulfobenzoic acid orsalts of sulfodicarboxylic acids and the salts of acetic acid, lacticacid, citric acid and tartaric acid.

Further, the water-soluble salts of higher molecular weightpolycarboxylic acids are useful as builders, especially polymcrizates ofmaleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,methylenemalonic acid and citraconic acid. Mixed polymcrizates of theseacids with one another or with other polymcrizable substances, as forexample with ethylene, propylene, acrylic acid, methacrylic acid,crotonic acid, 3butenecarboxylic acid, 3-methyl-3-butanecarboxylic acidand also with vinyl methyl ether, vinyl acetate, isobutylene, acrylamideand styrene, are also useful.

Of the usual washing agent additives, the water-soluble condensedphosphates, especially the pyro-, tripoly-or tetrapolyphosphates havespecial practical importance. They may be replaced by known organiccomplex-forming compounds or be combined with them.

The latter include, for example, nitrilotriacetic acid,ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriaceticacid, polyalkylene-polyamine-N- polyacetic acids and other known organiccomplex-forming compounds. Combinations of different complex-formingcompounds may also be used. Diand polyphosphonic acids of the followingconstitutions also belong to the other known complexforming compounds.

OH OH HO OH .O=P/ O=P/ \P=O O=P/ $11 (L\)H H \)H X OH X--C-H R- OHHOCRCOH N--( JP O OH OH HO OH \OH 3 O=P/ O=P/ \P=O 0:]?

\H on H H wherein R represents alkyl and R represents alkylene radicalswith one to eight, preferably one to four, carbon atoms, and X and Yrepresent hydrogen atoms or alkyl radicals with one to four carbonatoms. Carboxy-methylenephosphonic acid (HOOCCH PO(OH) is also useful asa complex-forming compound according to the invention. All thesecomplexforming compounds may be present as the free acids, but arepreferably present as the alkali metal salts.

The washing agents according to the invention are preferably used aswashing agents for white goods at boiling temperature or in the vicinityof the boiling temperature. They therefore often contain a bleachingcomponent based on active oxygen or active chlorine.

The bleaching agents based on active oxygen are, especially, theinorganic percompounds, for example, perpyrophosphates,perpolyphosphates, percarbonates and perborates. The commercial sodiumperborate of the approximate composition NaBO,-H O -3H O is ofparticular practical importance. Partly or completely dehydratedperborates that is up to the approximate composition NaBO -H O may alsobe used in its place. Finally, active oxygen containing borates, MaBO 'HO are also useful in which the ratio Na O B 0 is less than 05:1 andpreferably lies in the region of 0.4 to 0.15:1, and in which the ratio HO zNa lies in the region of 0.5 to 4:1. These products are described inGerman Pat. No. 901,287 and in U. S. Pat. No. 2,491,789. The perboratesmay be wholly or partly replaced by other inorganic per-compounds,especially peroxy-hydrates, such as for example, the peroxyhydrates ofortho-, pyroor poly-phosphates, for example of tripolyphosphates, andalso of the carbonates.

The active chlorine compounds useful as bleaching agents may beinorganic or organic. The inorganic active chlorine compounds includealkali metal hypochlorites, which may be used especially in the form oftheir mixed salts or addition compounds with orthophosphates orcondensed phosphates, as for example, with pyroand polyphosphates, orwith alkali metal silicates. If the washing agents and washing agentadjuvants contain monopersulfates and chlorides, active chlorine isformed in aqueous solution.

Suitable organic active chlorine compounds are, in particular, theN-chloro-compounds in which one or two chlorine atoms are linked to anitrogen atom, the third valency of the nitrogen atom being preferablylinked to a negative group, especially a CO or SO group. These compoundsinclude dichloroand trichloro-cyanuric acid, chlorinated alkylguanidesor alkylbiguanides, chlorinated hydantoin and chlorinated melamine.

The washing agents may also contain stabilizers for the bleachingcomponent, especially for the percompounds. The above-indicatedcomplex-forming compounds often have a stabilizing action. However, intheir place or together therewith, different kinds of stabilizers may bepresent, for example, those which act through their large surface area.These customary water-soluble or water-insoluble stabilizers areutilized in amounts up to percent, preferably from 0.25 percent to 8percent by weight.

Suitable water-insoluble stabilizers for per-compounds are the differentmagnesium silicates, mostly obtained by precipitation from aqueoussolutions, of composition MgO: SiO 4:1 to 1:4, preferably 2:1 to 1:2 andespecially 1:1. These magnesium silicates may be replaced by thecorresponding silicates of other alkaline earth metals or thecorresponding silicates of cadmium or tin. Hydrated oxides of tin arealso utilizable as stabilizers. These water-in-soluble stabilizers areusually present in amounts from 1 to 8 percent, preferably 2 to 7percent of the weight of the total preparation.

Suitable water-soluble stabilizers, which may be present together withwater-insoluble stabilizers, are the above referred-to organiccomplex-forming compounds, the amount of which may constitute 0.25 to 5percent, preferably 0.5 percent to 2.5 percent of the weight of thetotal preparation, depending on the strength of the complex formed.

The action of the bleaching components and above all of the percompoundscan be increased by known activators, such as small quantities of heavymetal ions, especially copper ions, which may preferably be present asmixed silicates of magnesium.

Furthermore, dirt carriers or soil suspension agents may be contained inthe washing agents according to the invention, which keep the dirt,detached from the fiber, suspended in the washing bath and thus preventgraying. For this purpose water-soluble colloids of mostly organicnature are suitable, as for example, the water-soluble salts ofpolymeric carboxylic acids, glue, gelatine, salts of ethercarboxylicacids or ethersulfonic acids or starch or cellulose or salts of acidsulfuric acid esters of cellulose or starch. Water-soluble polyamidescontaining acid groups are also suitable for this purpose. Further,starch and starch products other than those named above can be used, asfor example, degraded starch, aldehyde starches and so on.Polyvinyl-pyrrolidone is also utilizable. The enzymes which may beutilized may be obtained from animals, microorganisms such as bacteriaor fungi, and plants, especially from digestive ferments, yeasts andstrains of bacteria. They usually represent a complicated mixturecomposed of various enzymatic active substances. According to theiraction they are denoted as proteases, carbohydrases, esterases, lipases,oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases,transferases, desmolases or nucleases. The enzymatic substances obtainedfrom strains of bacteria or fungi, such as Bacillus subtilis andStreptomyces griseus, are of special interest. Further useful enzymesare pepsin, pancreatin, trypsin, papain and diastase. The enzymepreparations obtained from Bacillus subtilis, however, have theadvantage, as compared with the last-named enzymes, in that they arerelatively stable with respect to alkali, percompounds and anionicdetergents, and even at temperatures between 45 and 70 C are still notappreciable inactivated. Their relatively great stability towardsoxidizing agents possibly depends on their small content of freesulfhydryl groups.

The enzymes are marketed by the producers usually with addition ofblending agents. Suitable blending agents are sodium sulfate, sodiumchloride, alkali metal ortho-, pyroor polyphosphates, especiallytripolyphosphates. The still moist enzyme preparations are frequentlyincorporated with calcined salts, which then, in some cases withagglomeration of the particles present to larger particles, bind thewater present together with the enzymatic substance as water ofcrYstallization.

If the enzymatic substances are present as dry products, liquid orpaste-like non-ionic organic compounds, as for example, ethylene glycol,polyethylene glycols, butylene glycol or polybutylene glycols, and alsothe known liquid to pastelike surface-active compounds, which areobtained for example, by adding ethylene oxide and possibly propyleneoxide to the starting materials known for the preparation of suchproducts, can also be used for binding the enzymatic active substance tothe respective preparation to be made. For this purpose, a mixture ofthe components of the combination of surface-active compounds or of thewashing agent and the enzymatic substance, for example, is sprayed withthese nonionic products, or the enzymatic substance is dispersed in thesaid non-ionic substances and this dispersion is united with the otherconstituents of the product. If the other constituents of the productsare solids, the dispersion of the enzymatic substances in the non-ioniccomponent can be sprayed on the other solid constituents.

The components of the washing compositions according to the invention,especially the builders, are usually selected so that the preparationshave a neutral to distinctly alkaline reaction, so that the pH value ofa 1 percent solution of the preparation usually lies in the region of 7to 12. Fine washing compositions usually have a neutral to weaklyalkaline reaction (pH value 7 9.5), while soaking, prewashing andboiling washing compositions are made more strongly alkaline (pHvalue=9.5 12, preferably 10 12.5).

The brighteners which may be used are mostly, if not exclusively,derivatives of diaminostilbenesulfonic acid, diarlypyrazolines andaminocoumarins.

Examples of brighteners from the class of diaminostilbenesulfonic acidderivatives are compounds according to the formula.

in the formula R and R signify halogen atoms or alkoxy groups, aminogroups or residues of aliphatic, aromatic or heterocyclic, primary orsecondary amines, or residues of aminosulfonic acids, while aliphaticresidues present in the above groups preferably contain one to four andespecially two to four carbon atoms, and in the heterocyclic ringsystems, fiveor six-membered rings are usually concerned.

morpholino-, Nl-lC,,l-l -Nl-l-C H,SO H, OCH

Some of these brighteners are to be regarded as transitional types tothe cotton brighteners as regards their affinity for the fiber, forexample the brightener in which R equals NHC H The compound4,4-bis-(4-phenylvicinal-triazolyl-Z-)-stilbenedisulfonic acid-2,2 alsobelongs to the cotton brighteners of the diaminostilbenesulfonic acidtype.

Diarylpyrazolines of formulas [I1 and IV belong to the polyamidebrighteners, of which again a few have a certain affinity for cottonfibers:

I C Hz- H2 Ar1N t c -Ari R104: c-n

In formula III, R and R represent hydrogen atoms, or alkyl or arylresidues possibly substituted by carboxyl, carbonamide or ester groups.

R and R represent hydrogen or short-chain alkyl residues.

Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl,which may carry further substituents such as hydroxy, alkoxy,hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acidester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms.

Brighteners of this type found at present on the market are derived fromthe formula IV, and the residue R may represent the groups Cl,-SO,-Nl-l,, SO,-CH CH and COO--CH --CH,OCH while the residue R in allcases represents a chlorine atom. 9-Cyano-anthracene is also on themarket as a polyamide brightener.

In addition, aliphatic or aromatic substituted amino coumarins belong tothe polyamide brighteners, for exan' pie 4- methylJ-dimethylaminoor4-methyl-7dimethylaminocoumarin. Further useful polyamide brightenersare the compoundsl-(benzimidazolyl-2')-2-(N-hydroxyethylbenzimidazolyl-2')-ethylene andl-N-ethyl-3-phenyl-7- diethylamino-carbostyril. Suitable brighteners forpolyester and polyamide fibers are the compounds 2,5-di-(benzoxazolyl-2)-thiophene and 1,2-di-(5 -methyl-benzoxazolyl-2' ethylene.

The following examples are illustrative of the practice of theinvention. However, they are not to be deemed limitative in any manner.

EXAMPLES The following examples describe the compositions of some of thecombinations of surface-active compounds according to the invention or afew washing agents with a content of such surface-active combinations.in them:

ABS is the alkali metal salt of an alkylbenpene-sulfonic acid with 10 to15, preferably ll to 13, carbon atoms in the alkyl chain, obtained bycondensing straight chain olefins with benzene and sulfonating thealkylbenzene so obtained.

Olefinsulfonate" is an alkali metal sulfonate obtained from straightchain olefins 12 to 16 carbon atoms) with terminal or non-terminaldouble bonds by sulfonation with S0, and hydrolysis of the sulfonationproduct with an alkali liquor. The

said sulfonate consists substantially of alkene sulfonate andhydroxyalkane sulfonate, but also contains small quantities of alkanedisulfonates. Each olefinsulfonate-containing preparation was preparedusing two different types of olefinsulfonate; one was from a mixture ofstraight-chain terminal olefins, and the other was prepared from amixture of non-terminal olefins.

Alkane sulfonate is an alkali metal sulfonate obtained from paraffmswith 12 to 16 carbon atoms by the sulfoxidation method.

Fatty acid ester sulfonate is an alkali metal sulfonate obtained fromthe methyl ester of a hardened tallow fatty acid by sulfonating with S0Oleyl alcohol ether sulfate or Tallow alcohol ether sulfate or Coconutalcohol ether sulfate are the sulfated products of addition of 2 mols ofethylene oxide (E0) to l mol of oleyl alcohol or of 3 mols of ethyleneoxide to 1 mol of tallow fatty alcohol or of 2.5 mols of ethylene oxideto 1 mol of coconut fatty alcohol.

Tallow alcohol sulfate" or Coconut alcohol sulfate" are the alkali metalsalts of the sulfated fatty alcohols prepared by reduction of tallowfatty acid or coconut fatty acid.

Oleyl alcohol 5 E0" or Oleyl alcohol 10 B0" are the products of additionof five or 10 mols of ethylene oxide to one mol of a commercial oleylalcohol.

Coconut alcohol +20 E0" is the product of addition of 20 mols ofethylene oxide to 1 mol of a fatty alcohol prepared from coconut fattyacid.

Coconut alcohol +9 E0 +12 PO" is the product of addition of 9 mols ofethylene oxide to 1 mol of a fatty alcohol prepared from coconut fattyacid, reacted with 12 mols of propylene oxide.

Fatty acid monoethanolamide 8 E0" is the product of addition of 8 molsof ethylene oxide to 1 mol of a monoethanolamide of coconut fatty acid.

Dioctylacetate" is the alkali metal salt of di-octylacetic acid(a-n-octyl-capric acid).

Dicoconut alkylaminopropionate" is the carboxylic acid salt of an alkalimetal obtained from the corresponding dialkylamine (prepared fromcoconut fatty acid) by reacting with methyl acrylate and saponifying thereaction product.

CMC" is the alkali metal salt of carboxymethyl-cellulose.

EDTA" is the alkali metal salt of ethylenediaminetetraacetic acid.

NTA" is the alkali metal salt of nitrilotriacetic acid.

Waterglass is a silicate of the composition Na O.3.3SiO

Perborate" is a product of the approximate composition NaB -H,O,-H,Ocontaining about 10 percent of active oxygen.

Cotton Brightener is the commercial product Blankophor BBl-l/Sll"Polyamide Brightener is the commercial product Purwil P71 PolyesterBrightener l" is the commercial product Uvitex SOF."

Polyester Brightener ll" is the commercial product Calcolluor whiteALF."

The composition of the fatty acid mixtures from which the various soapscontained in the combinations of surface-active compounds or washingagents were produced, may be taken from the following Table I:

TABLE I Composition of the Fatty Acid Mixtures Corresponding to theSoaps No. of carbon atoms in the fatty acid Wt. percent of fatty acidcomponent in the soap 818 1018 1022 1218 1222a 1222b lmu 1622 1822Iodine value of the fatty acid mixture Unless specified to the contrary,the anionic surface-active compounds and the other salts are present asthe sodium salts. All percentages given are by weight.

In the examples, the foam inhibitor is associated with the combinationof surface-active compounds. This is incorrect in so far as the specialfoam inhibitors mentioned in the description are not regarded assurface-active compounds. They are nevertheless listed together with thecombinations of surfaceactive compounds because they do of courseinfluence the 1 foaming capacity of the surface-active compounds. in thepreparation of the products, the foam inhibitor used in each case,dissolved in a suitable organic solvent or in the molten state, wassprayed by means of ajet nozzle on the agitated pulverulent combinationof surface-active compounds or on the agitated pulverulent washingagent. if combinations of surface-active compounds which containsynthetic sulfates or sulfonates together with soap are concerned,paraffin or paraffin oil, for example, are suitable foam inhibitors. 1nExamples 1-8, an N,N',N"--trialky1melamine was used as foam inhibitor.This foam inhibitor could be replaced, with a similar result, by abis-(alkylamino)-monochlorotriazine or by a mixture of percent to 90percent of the melamine derivative and 90 to 10 percent of thechlorotriazine derivative. in all these triazine derivatives, the alkylresidues were present as mixtures of homologs with eight to 18 carbonatoms. Their foam inhibiting action commenced at temperatures of about50 C and was present to the full extent after a temperature of 65 C wasexceeded.

in the preparations according to Examples 9 to 21, a mixture of about 45percent of a di(alkylamino)- monochlorotriazine and about 55 percent ofan N,N,N-trialkylmelamine was used as foam inhibitor. In all thesetriazine derivatives the alkyl residues were present as a mixture ofhomologs with eight to 18 carbon atoms. 1f the combinations ofsurface-active compounds described in the examples contain syntheticsulfates and/or sulfonates together with soap, the said aminotn'azinederivatives can be replaced by the other above-mention foam inhibitorswhich are non-surface-active compounds.

1f the preparations herein described the enzymefree and also theenzyme-containing preparations are prepared in a pourable state (i.e.,as powder, granules, agglomerates), it is advisable to mix thenon-surface-active foam inhibitors with the pourable preparations orparts thereof. This can also be carried out by spraying the foaminhibitor present in the liquid state on the agitated pourable productor a part thereof. The foam inhibitors may then be mixed as discreteparticles with the other constituents of the product, while they arealso combined with the particles of the preparation and can wholly orpartly cover these. If the said preparations are prepared as pastes, itis then advisable to incorporated the foam inhibitors as solid powder orgranules in the pastes without their granular size being therebysubstantially reduced.

The following Examples 1 to 21 describe different combinations ofsurface-active compounds with a content of textile softeners accordingto the invention.

EXAMPLE la 42% ABS 14% Oleyl alcohol 10 E0 6% Soap 1822 38%Dioctylacetate EXAMPLES lb AND 1c EXAMPLE 2 37% ABS 17% Oleyl alcohol 10E0 46% Dioctylacetate EXAMPLE 3 44% ABS 14% Oleyl alcohol 10 E0 4% Soap1622 38% Dioctylacetate EXAMPLE 4 34% ABS 13% Fatty acid ethanolamide 8E0 20% Soap 1222 y.

33% Dioctylacetate EXAMPLE 5 48% Coconut fatty alcohol 20 E0 25% Coconutfatty alcohol+9 EO+12 P0 27% Dioctylacetate EXAMPLE 6 49% ABS 16% Oleylalcohol 10 E0 33% Dioctylacetate 2% Foam inhibitor EXAMPLE 7 32% Olefinsulfonate 16% Oleyl alcohol 10 E0 15% Soap 1218 34% Dioctylacetate 3%Foam inhibitor EXAMPLE 8 32% Olefin sulfonate 16% Oleyl alcohol 10 E014% Soap 1222 a 34% Dioctylacetate 4% Foam inhibitor EXAMPLE 9 37% ABS17% Oleyl alcohol 10 E0 43% Branched-chain tertiary carboxylic acidtextile softener 3% Foam inhibitor EXAMPLE 10 33% ABS 1 1% Tallowalcohol sulfate 14% Oleyl alcohol 10 E0 4% Soap 1622 38% Branched-chaintertiary carboxylic acid textile softener.

EXAMPLE 11 30% ABS 13% Fatty acid monoethanolamide 8 E0 20% Soap 1222 [L32% Branched-chain tertiary carboxylic acid textile softener 5% Foaminhibitor EXAMPLE 12 35% Fatty acid ester sulfonate 14% Coconut alcoholsulfate 16% Oleyl alcohol 10 E0 33% Branched-chain tertiary carboxylicacid textile softener 2% Foam inhibitor EXAMPLE 13 34% ABS 8% Coconutalcohol sulfate 3% Tallow alcohol sulfate 18% Oleyl alcohol 10 E0 34%Branched-chain tertiary carboxylic acid textile softener 3% Foaminhibitor EXAMPLE 14 34% ABS 9% Coconut alcohol sulfate 10% Oleylalcohol 10 E0 9% Soap 1218 34% Branched-chain tertiary carboxylic acidtextile softener 3% Foam inhibitor EXAMPLE 15 26% ABS 7% Coconut alcoholsulfate 2% Tallow alcohol sulfate 8% Coconut alcohol ether sulfate 22%Soap 1222 35% Branched-chain tertiary carboxylic acid textile softener 7EXAMPLE 16 18% Fatty acid ester sulfonate l 1% Coconut alcohol sulfate9% Oleyl alcohol E0 28% Soap 1222 34% Branched chain tertiary carboxylicacid textile softener EXAMPLE 17 40% Alkane sulfonate 9% Coconut alcoholsulfate 14% Oleyl alcohol E0 35% Branched-chain tertiary carboxylic acidtextile softener 2% Foam inhibitor EXAMPLE 18 Olefin sulfonate 10%Tallow alcohol sulfate 14% Oleyl alcohol 10 E0 27% Soap 1222 29%Branched-chain tertiary carboxylic acid textile softener EXAMPLE 19 10%Coconut alcohol sulfate 20% Oleyl alcohol ether sulfate 24% Oleylalcohol 5 E0 23% Soap 1222 23% Branched-chain tertiary carboxylic acidtextile softener EXAMPLE 20 5% Coconut alcohol sulfate 5% Tallow alcoholsulfate 25% Tallow alcohol ether sulfate 14% Oleyl alcohol 5 E0 14% Soap1018 34% Branched-chain tertiary carboxylic acid textile softener 3%Foam inhibitor EXAMPLE 21 41% ABS 9% Coconut alcohol sulfate 17% Coconutalcohol ether sulfate 31% Branched-chain tertiary carboxylic acidtextile softener 2% Foam inhibitor The dioctylacetate used in Examples 1to 8 and the branched-chain tertiary carboxylic acid used in Examples 9to 21 are interchangeable and each can also be replaced with similarresults by the nitrogen-containing branched-chain carboxylic acids.

The combinations of surface-active compounds described in the Examples 9to 21 contain as textile softeners, salts of carboxylic acid mixtureswith the carbon number indicated below, which were prepared by additionof carbon and water to mixtures of substantially aliphatic olefins.

Textile softener C 1,: salt of a C carboxylic acid Textile softener C fsalt of a C, carboxylic acid Textile softener C 3,: salt of a Ccarboxylic acid The Examples 1 to 21 describe combinations ofsurface-active compounds which are provided as special productspreferably for the laundry trade or the textile industry. The

combinations of surface-active compounds described in Examples 1 to 21come on the market mostly in admixture with sodium sulfate or with othercustomary washing composition additives, and the combinations ofsurface-active compounds may constitute to 50 percent by weight and theother constituents 10 to 50 percent by weight.

In all the Examples the data for the surface-active compounds relate tothe pure active substance; in the case of the textile softeners, smallamounts of by-products from the preparation may also be present.

in the following Examples the sign in the lines "Na SO means that smallamounts of sodium sulfate which have been introduced by the anionicsurface-active compounds used are present as impurity. The residueconsists substantially of water, and also includes dyes and perfumes.When the amount of Na SQ, is indicated with the residue also includesthe sodium sulfate present.

The following examples describe a few washing agents which containcombinations of builders and additives in addition to the combinationsof surface-active compounds according to Examples 1 to 21.

EXAMPLE 22 19% Combinations of surface active compounds according toExamples 1 to 12 4.5% Na=O'3.3 SiO,

1.0% MgSiO 1.5% CMC 16% Pcrborate Remainder: Brightener, perfume, sodiumsulfate and water.

EXAMPLE 23 20.8% Combination of surface-active compounds according toExamples 1 to 12 2.5% MgSiO;

0.8% CMC 31.3% Perborate Remainder: Brightener, perfume, sodium sulfateand water EXAMPLE 24 17.5% Combination of surface-active compoundsaccording to Examples 1 to 12 18.0% NTA 6.6% Hydroxyethanediphosphonate19.0% Mango 4.0% Na,0- 3.3 SiO 1.6% MgSiO,

1.3% CMC 21.0% Perborate Remainder: Brightener, perfume, sodium sulfateand water.

EXAMPLE 25 19.5% Combination of surface-active compounds according toExamples 1 to 12 19.0% NTA 14.0% Hydroxyethanediphosphonate 12.0% NaP,O,

4.5% NaO,- 3.3 S10, 1.0% MgSiQ 1.5% CMC 16.0% Perborate Remainder:Brightener, perfume, sodium sulfate and water.

EXAMPLE 26 27.5% Combination of surface-active compounds according toExamples 1 to 12 32.0% Na,P,O 28.0% Hydroxyethanediphosphonate 7.5% NaO' 3.3 SiO 1.6% MgSiO,

1.3% CMC Remainder: Brightener, perfume, sodium sulfate and water.

EXAMPLE 27 23.8% Combination of surface-active compounds according toExamples 1-12 6.5% Na.P O, 38.0% Na P O 5.5% Na,0- 3.3 SiO 2.0% MgSiO1.2% CMC 7.0% Perborate Remainder: Brightener, perfume, sodium sulfateand water.

EXAMPLE 28 EXAMPLE 29 18.2% Composition of Example 13 +Na SO 30.0% Na PO,O

0.2% EDTA 6.0% Na O 3.3 SiO 2.5% MgSiO 2.0% CMC 0.3% BrightenerRemainder: Perfume, sodium sulfate and water EXAMPLE 30 23.2%Composition of Example 14 +Na,SO 35.0% Na l o 0.3% EDTA 4.5%Na O- 3.3510 1.8% CMC 0.8% Brightener 27.0% Perborate Remainder: Perfume, sodiumsulfate and water EXAMPLE 31 19.9% Composition of Example 15 +Na,SO28.0% Na P O 15.0% NTA 0.22% Hydroxyethane diphosphonate 5.0% Na O' 3.3SiO 2.0% MgSiO 1 .3% CMC 0.8% Brightener 24.0% Perborate Remainder:Perfume, sodium sulfate and water EXAMPLE 32 23.2% Composition ofExample 16 +Na SO 8.0% N co, 24.0% Na,1;,0

5.0% NTA 0.25% EDTA 4.0% Na O- 3.3 SiO,

1.9% CMC 0.4% Brightener 25.0% Perborate Remainder: Perfume, sodiumsulfate and water EXAMPLE 33 19.5% Composition of Example 17 +Na,SO

38.0% Na l 0 0.5% EDTA 3.8% Na O- 3.3 SiO 1.2% CMC 0.9% Brightener 23.5%Perborate Remainder: Perfume, sodium sulfate and water EXAMPLE 34 26.2%Composition of Example 18 21.0% Na,,P O

Remainder: Perfume and water EXAMPLE 35 Perborate Remainder: Perfume andwater EXAMPLE 36 21.1% Composition of Example 20 18.0% Na SO 35.0% Na P-,O 10.0% NTA 3.7% Na O' 3.3 SiO 1.7% CMC Remainder: Perfume and WaterEXAMPLE 37 30.0% Composition of Example 21 10.0% Na,SO 48.0% Na -,P;,O

4.5% Na O- 3.3 $10 1.7% CMC Remainder: Perfume and water EXAMPLE 38Brighteners for cotton, polyamides or polyesters or combinations therofare used, depending upon the purpose for which the washing compositionis to be used.

The washing compositions described in Examples 22 to 38 were preparedwith addition of enzymes. The enzymes were commercial products which hadbeen adjusted by the manufacturer to the following activities byaddition of 7 to 15 per cent by weight of sodium sulfate:

A protease with 125,000 LVE/g An amylase with 75,000 SKBE/g A lipasewith 10,000 lE/g 1n the following list the enzyme activity, referred to1 g of the finished washing composition, is given in addition to thequantity of enzyme:

1. A washing composition according to one of the Examples 22 to 38contains 0.3 to 1.5 percent by weight of protease (375-1875 LVE/g) 11. Awashing composition according to one of the Examples 22 to 38 contains1.2 percent by weight oflipase lE/g) 111. A washing compositionaccording to one of the Examples 22 to 38 contains 0.4 percent by weightof protease (500 LVE/g) 1.0 percent by weight of amylase (750 SKBE/g)IV. A washing composition according to one of the Examples 22 to 38contains 2.0 percent by weight of amylase (1,500 SKBE/g) V. A washingcomposition according to one of the Examples 22 to 38 contains 0.2percent by weight of protease (250 LVE/g) 0.5 percent by weight ofamylase (.375 SKBE/g) 0.5 percent by weight of lipase (50 lE/g) VI. Awashing composition according to one of the Examples 22 to 38 contains1.0 percent by weight of protease (1,250 LVE/g) 0.3 percent by weight ofamylase (225 SKBE/g) 0.4 percent by weight of lipase (40 IE/g) Thetextiles washed with the washing comPositions according to theinvention, especially those of cotton or linen, show a remarkablypleasant and soft handle; cotton towelling is more voluminous than whenit is washed without use of the textile softeners according to theinvention.

All the combinations of surface-active compounds or washing agents witha content of such surface-active combinations described in the Exampleshave a low foaming power and are therefore suitable for use in washingmachines. However, it may occasionally happen, depending on the localconditions, which cannot be influenced by the washing agentmanufacturer, as for example, the concentration of the washing agentused, hardness of the water, quantity and nature of the dirt in thelaundry to be washed and so on, that the combinations of surface-activecompounds or the washing agents containing them foam somewhat more thanis desirable. In such cases the foaming power of the preparations of theExamples can be reduced still further by addition of larger amounts offoam inhibitor and/or by increasing the content of soaps of saturatedfatty acids with 18 to 22, preferably'20 to 22, carbonatoms.

.Textiles washed with the combinations of surface-active compoundsaccording to the invention or with washing agents containing thesesurface-active combinations, especially those made of cotton or linen,show a remarkably pleasant and soft handle. Cotton terry cloth is morevoluminous than when it is washed without the use of the textilesoftener according to the invention.

EXAMPLES 39 to 50 The technical effect obtained according to theinvention can be demonstrated numerically in a test method developedspecially for this case. This method depends on the measurement of theresistance to traction when a curtain tape is frilled or gathered. Thecurtain tape shown in FIG. 1 consists of a woven band 1 about 2 cm inwidth. Through it in the longitudinal direction are drawn the interwovencotton cords 2. If the cords at one end of the band are held fast andthe cloth is pushed along on the cords, a specific force has thereby tobe applied. This force increases with the hardness of the curtain tapesused.

The pieces of band about 20 cm long intended for the test were firstwashed successively 20 times, with a bath ratio of 1 l5 and aconcentration of washing agent of 5 g per liter in water of 17 dH, at amaximum temperature of 98 C. An impeller washing machine was used forthese experiments, and the curtain tape was immersed in the bath duringthe whole time of treatment.

By this pre-treatment, the dressing, which is usually applied during thefinishing of the textile, was removed without residue from the curtaintapes. Since the washing agents contained no textile softener, thecurtain tapes were also hardened by the pre-treatment. Then some of thecurtain tapes so pre-treated were washed in the same way successively 5times with the washing agents according to the invention, while in thecase of the remainder a washing agent of similar composition was usedfor comparison, which of course contained, instead of the textilesoftener, the same amount by weight of sodium sulfate. Each curtaintape, therefore, had to pass through 25 washing operations.

The curtain tapes were dried and before the test measurements, wereconditioned at 65 percent relative humidity and 20 C. Beforemeasurement, the tape, but not the two cords, was cut at about 2 cm fromoneend of the band'(see FIG. 1). This end of the band was now (see FIG.2) inserted in the top clamp 3 of a tensile-testing machine, while thelower clamp was replaced by the gripper 4, which was inverted over thelower cut edge of the cut mentioned. The two inter-woven cords 2 werepassed through two notches 5 in the grip-per. The gripper was thenpulled down 5 cm in the tensile testing machine. The tape then slippedalong on the cords, and the force thereby applied was measured on thetop clamp. For each washing agent tested, drawing experiments on 20tapes were made and the values thus obtained were averaged. Thedifference between the values obtained with the comparative washingagent and with the washing agents including the softeners according tothe invention is a measure of the softening effect obtained.

The composition of the washing agent used in the Examples and thesoftness the tapes attained when treated according to the invention aregrouped in the following Table II. The values so obtained are onlycomparable when the treatment with the different washing agents hastaken place as far as possible under constant conditions, and especiallywhen the separate pieces of the curtain tape come from a singlemanufactured web. If curtain tapes from webs of different manufacturersare used for the test, or as was the case in Examples 39-1-40, 41-44,45+46 and 47-50, curtain tapes of different origin or character areused, a comparison is only admissible in the case of results coming fromthe one series of experiments. In the following Table the comparativeexperiments made with washing agents without a softener are denoted asV, and as an index, the numbers of those examples in which a comparisonis allowable are associated with this letter.

' TABLE II Composition of the Washing Agents Used in the ComparativeExperiments and the Results of the Experiments Percent wt. of componentin washing agent according to example active compounds:

ABS 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Oleyl alcohol plus COONa 7.5 7.5(Coconuth CH COONa" 7.5 7.5 (C|2H1s)2 N 7.5 7. 5

NaOOCC2H4C 0 Washing agent builders:

N PO 1. 8 2. 3 6. 5 20. 2 38. 0 23.8 6. 5 5. 5 2. 0 2. 0 1. 2 1, 2NnBO2-H2O2-3 H2O 17. 0 17. O Nit-2804, brightener,

perfume, watcr Remainder Remainder Improvement of the softness 454 342174 61 05 37 *Cocormt means here an alkyl residue formed by reduction ofthe fatty acids derived from coconut fat.

Composition of the Washing Agents Used in the Comparative Experimentsand the Results of the Experiments Percent by wt. of component in thewashing composition according to example Washing composition V Vcomponent 45 46 45-1-46 47 48 40 50 45-60 Table ll -ContinuedComposition of the Washing Agents Used in the Comparative Experimentsand the Results of the Experiments Percent by wt of component in thewashing composition according to example It is clearly apparent,however, that the softness attained increases with the chain length ofthe branched chain carboxylic acids used as textile softeners, at'leastin the carbon number range of 9 to 21. The desired effect is furtherimproved by simultaneous presence of soaps of higher fatty acids, espe-20 cially those containing 18 to 22 carbon atoms.

If the textile softener contained in the combinations of surface-activecompounds in the Examples is replaced by the following compounds similarresults are obtained. Coconut" here means an alkyl residue formed byreduction of the fatty acids derived from coconut fat.

The following examples demonstrate the washing preparations containingthe combination of surface-active compounds of the invention incombination with enzyme systems.

As enzymes, the following commercial products were used which wereadjusted by the manufacturer to the following activities by addition ofsodium sulfate in amounts of about 7 percent:

A protease with 120,000 LVE/gm An amylase with 75,000 SKBE/gm A lipasewith 10,000 IE/gm in the Examples, in addition to the amount of enzyme,the enzyme activity is also given, based on 1 gm of washing agent.

EXAMPLE 51 An all purpose washing agent, which at temperatures of about45 C has a certain development of foam, but with increasing temperatureshows inhibition of foaming which becomes greater and greater, so thatit can be used even at boiling temperatures, has the followingcomposition:

6.7% ABS 0.5% Tallow alcohol sulfate l.5% Coconut alcohol sulfate 3.0%Oleyl alcohol 10 E0 05% Foam inhibitor 6.0% Dioctylacetate 2.0% CMC 0.2%EDTA 30.0% Na. .P,O

6.0% Waterglass 2.5% MgSiO, 0.25% Cotton Brightener 0.03% PolyarnideBrightener 32.0% Perborate 0.8% Protease (i000 LVE/g) Remainder: bluedyestuff, perfume and water EXAMPLE 52 All purpose washing agent asexample 5i .l% ABS .0% Coconut alcohol sulfate .5% Oleyl alcohol 10 E02.0% Soap 818 .6% Foam inhibitor EXAMPLE 53 All purpose washing agent asexample 51 5.5% ABS l.5% Coconut alcohol ether sulfate 0.3% Tallowalcohol sulfate l.2% Coconut alcohol sulfate 42% Soap 1222 b 7.2%Dicoconut alkylaminopropionate 1.3% CMC 0.22% EDTA 15.0% NTA 28.0%Na,P,O

5.0% Waterglass 2.0% MgSiO 0.5% Cotton Brightener 0.05% PolyarnideBrightener 0.2% Polyester Brightener II 24.0% Perborate 0.4% Protease(500 LVE/g) 1.0% Amylase (750 SKBE/g) Remainder: perfume and waterEXAMPLE 54 All purpose washing agent as example 5l 4.6% Fatty acid estersulfonate 2.3% Coconut alcohol sulfate 2.0% Oleyl alcohol 5 E0 6.3% Soap1022 8.0% Dicoconut alkylaminopropion ate 1.9% CMC 0.25% EDTA 5.0% NTA24.0% Na,P O,

8.0% Na,C0,

4.0% Waterglass 0.4% Cotton Brightener 0.04% Polyarnide Brightener 25.0%Perborate l.5% Protease (1875 LVE/g) Remainder: perfume and waterEXAMPLE 55 EXAMPLE 56 All purpose washing agent as example Sl 5.5%Olefin sulfonate 2.5% Tallow alcohol sulfate 3.5% Oleyl alcohol l0 E07.2% Soap 1022 7.5% Dioctylacetate .4% CMC 0.

. Na,P,,0,,, .2% Waterglass 3.0% MgSiO,

0.35% Cotton Brightener 0.03% Polyamide Brightener 0.7% PolyesterBrightener 11 22.0% Perborate 0.8% Protease (1000 LVE/g) Remainder:perfume and water EXAMPLE 57 For use for washing colored andeasy-carefabrics, washing agents specified for use at temperatures up to60 C, but which also possess a'sufficient inhibition of foaming attemperatures up to 100 C are preferred.

9.8% Oleyl alcohol ether sulfate 1.8% Coconut alcohol sulfate 5.0% Oleylalcohol 5 B 5.0% Soap 1222 b 5.0% Dioctylacetate 1.5% CMC 33.0

3.5% Waterglass 5.0% Na SO, 22.0% Perborate 0.3% Protease (375 LVE/g)Remainder: perfume and water EXAMPLE 58 For washing easy-care textiles,washing agents'specified for use at temperatures up to 60C, but alsosafe from foaming at temperatures up to 100 C, are preferred.

EXAMPLE 59 Thiswashing agent has the same field of application as theproduct according to Example 58.

12.9% ABS 5.0% Coconut alcohol ether sulfate 2.5% Coconut alcoholsulfate 9.0% Dicoconut alkyl aminopropionate 1.7% CMC 48.0% Na,,P ,O,,,

4.5% Waterglass 10.0% Na SO,

0.2% Protease (250 LVE/g) 0.5% Amylase (375 SKBE/g) 0.5% Lipase (50lE/g) Remainder: perfume and water EXAMPLE 60 Prewashing agent, whichcan be used in case of need also at boiling temperatures without causingexcessive foaming.

1.0% Oleyl alcohol 5 B0 7.0% Oleyl alcohol E0 0.3% Foam inhibitor 3.0%Dioctylacetate 1.6% CMC 0 5% EDTA 4 0% Na P,O,

4 0% Waterglass 0 3 Cotton Brightener' 0.05% Polyamide Brightener 22.0%Sodium sulfate 0.6% Protease (750 LVE/g) 0.3% Amylase (225 SKBE/g) 0.4%Lipase (40 lE/g) Remainder: perfume and water When textiles, especiallycotton textiles, which are soiled with albumen, starch andfat-containing contaminations, are washed with the combinations ofsurface-active compounds or with the washing agents containing themaccording to the invention, the enzymes contained therein effect a morerapid removal of these contaminations, even at relatively lowtemperatures, especially when they are present as dried spots of blood,pus, gravy and so forth. The textile softeners contained in the productsaccording to the invention can then act on the textiles at a relativelyearly state in the washing process. Therefore, a combined action of theenzymes and the textile softeners is attained.

[t is quite possible to market the combinations of surfaceactivecompounds with a content of enzymes, rather than the finished washingagents. The formulations of such enzyme containing combinations ofsurface-active compounds follow directly from the above examples byomission of the builders and additives (CMC to perborate, as well asdyestuff and perfume). Of course, it is possible to incorporate buildercomponents in smaller quantities, such as for example, dirt carriers(CMC), complex-forming compounds (EDTA) and brighteners, to be alsopresent in the combinations of surfaceactive compounds. In the case ofExample 29, these combinations of surface-active compounds are presentas a paste, taking into consideration the large quantities of non-ionicsin the formulation.

The preceding specific embodiments are illustrative of the practice ofthe invention. It is to be understood, however, that other expedientsknown to those skilled in the art may be employed without departing fromthe spirit of the invention or the scope of the appended claims.

We claim:

1. A combination of surface-active compounds in granular or pasty formutilizable in neutral to alkaline textile washing baths which consistsessentially of (a) from 20 to 90 percent by weight of customarysurface-active compounds utilizable in neutral to alkaline textilewashing baths consisting of a mixture of anionic surface activecompounds selected from the group consisting of surface-activesulfonates, surface-active sulfates and straight-chain fatty acid soaps,and non-ionic surface-active compounds, and (b) from to 10 percent byweight of a textile softener selected from the group consisting of (1)compounds of the formula wherein R, and R are alkyl having from six to18 carbon atoms and n represents an integer from 0 to 2, and (2)watersoluble salts thereof.

2. The combination of surface-active compounds of claim 1 whereincomponents (a) are present in an amount of from 75 to 35 percent byweight and components (b) are present in an amount of from 25 to 65percent by weight.

3. The combination of surface-active compounds of claim 1 wherein R, andR are different and one of R, and R contains not more than twice as manycarbon atoms as the other of R, and R 4. The combination ofsurface-active compounds of claim 3 wherein one of R, and R contains notmore than 1.5 times as many carbon atoms as the other of R, and R 5. Thecombination of surface-active compounds of claim 1 wherein the sum ofthe carbon atoms in R, and R is between 14 and 20.

6. The combination of surface-active compounds of claim 1 wherein atleast 50 percent of said mixture of anionic surfaceactive compounds andnon-ionic surface-active compounds of component (a) is said anionicsurface-active compounds selected from the group consisting ofsurface-active sulfonates, surface-active sulfates and straight-chainfatty acid soaps.

7. The combination of surface-active compounds of claim 1 wherein atleast part of said mixture of anionic surface-active compounds andnon-ionic surface-active compounds of component (a) is saidstraight-chain fatty acid soap and the fatty acids present in said soapconsist of at least 50 percent of saturated fatty acids with from 16 to30 carbon atoms, wherein foaming of said combination of surface-activecompounds in water is reduced at higher temperatures.

8. The combination of surface-active compounds of claim 7 wherein atleast 3 percent of said fatty acids in said soap have from 20 to 30carbon atoms.

9. The combination of surface-active compounds of claim 7 wherein atleast percent of said fatty acids in said soap have from 20 to 30 carbonatoms.

10. The combination of surface-active compounds of claim 1 wherein afurther content of enzymes is present selected from the group consistingof proteases, amylases, lipases and mixtures thereof, wherein theenzymatic activity is in the range of 62.5 to 50,000 LVE per gram of thecombination of surface-active compounds in the case of proteases, of 25to 50,000 SKBE per gram of the combination of surface-active compoundsin the cases of amylases and of 2.5 to 10,000 IE per gram of thecombination of surface-active compounds in the case of lipases.

11. Washing agents and washing agent adjuvants containing from 5 to 80percent by weight of the combination of surfaceactive compounds of claim1 and from 20 to 95 percent by weight of a builder selected from thegroup consisting of neutral to alkaline reacting inorganic has beeninserted therefor.

12. The washing agents and washing agent adjuvants of claim 11containing from 15 to 40 percent by weight pf said combination ofsurface-active compounds and from 85 to 60 percent by weight of saidbuilders.

13. The washing agents and washing agent adjuvants of claim 12 whereinat least 30 percent by weight of said builder is selected from the groupconsisting of condensed alkali metal phosphates and organic builders.

l4. Washing agents in powder to granular form containing a compatibletextile softener consisting of (a) from 12 to 30 percent by weight of acombination of surface-active compounds consisting of (1) 25 to 65percent by weight of surface-active compounds selected from the groupconsisting of sulfonates and sulfates, (2) 5 to 40 percent by weight ofnon-ionic surface-active compounds, (3) to 50 percent by weight ofstraight-chain fatty acid soap, (4) 25 to 65 percent by weight of atextile softener selected from the group consisting of (i) compounds ofthe formula R2 I wherein R and R; are alkyl having from six to 18 carbonatoms and n represents an integer from 0 to 2, and (ii) watersolublesalts thereof, (5) 0.5 to 5 percent by weight of non-surface-active foaminhibitors effective at temperatures of 60 C selected from the groupconsisting of N-alkylated aminotriazines and aminotriazine adducts withpropylene oxide and/or butylene oxide containing from 10 to 100polyglycol units; (b) 40 to percent by weight of builders, at least partof the builders being alkaline reacting, said builders weighing from 1to 5 times that of component (a); and (c) 3 to 30 ercent by weight ofsoil sus ension a ents 5. The washing agents of 0 arm 14 w ereln afurther content of enzymes is present selected from the group consistingof proteases, amylases, lipases and mixtures thereof wherein theenzymatic activity is in the range of 50 to 5,000 LVE per gram of totalwashing agent in the case of proteases, of 20 to 5,000 SKBE per gram oftotal washing agent in the case of amylases and of 2 to 1,000 [E pergram of total washing agent in the case of lipases.

16. The washing agents of claim 14 wherein said non-surface-active foaminhibitors of component (a) (5) is incorporated with solid particles ofthe washing agent with said foam inhibitors surrounding at leastpartially said solid particles.

17. Prewashing agents in powder to granular form containing a compatibletextile softener consisting of (a) from 5 to 8 percent by weight of acombination of surface-active compounds consisting of (1) 25 to 65percent by weight of surface-active compounds selected from the groupconsisting of sulfonates and sulfates, (2) 5 to 40 percent by weight ofnonionic surface-active compounds (3) 10 to 50 percent by weight ofstraight-chain fatty acid soap, (4) 25 to 65 by weight of a textilesoftener selected from the group consisting of (i) compounds of theformula wherein R and R; are alkyl having from six to 18 carbon atomsand (ii) water-soluble salts thereof, (5) 0.5 to 5 percent by weight ofnon-surface-active foam inhibitors effective at temperatures over 60 Cselected from the group consisting of N-alkylated aminotriazines andaminotriazine adducts with propylene oxide and/or butylene glycolcontaining from 10 to 100 polyglycol units and (b) from to 92 percent ofbuilders.

18. The prewashing agents of claim 17 wherein a further content ofenzymes is present selected from the group consisting of proteases,amylases, lipases and mixtures thereof wherein the enzymatic activity isin the range of 50 to 5000 LVE per gram of total washing agent in thecase of proteases, of 20 to 5,000 SKBE per gram of total washing agentin the case of amylases and of 2 to 1,000 [B per gram of total washingagent in the case of lipases.

UNITED STATES PATENT oEETtE CERTIFICATE 0F QURRECTWN Patent No. Dateduly 97 Inventofls) Walter Fries, et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Claim 114.; after "and (0)" it should read to 35% by weight of bleachingcomponents Signed and sealed this 26th day of February l97L (SEAL) I rmAttest:

EDWARD M.FLETCHER,JR. MARSHALL DANN Attesting Officer Commissioner ofPatents FORM PO-105O (IO-69) USCOMM-DC 60376-P69 flu.s. GOVERNMENTPRINTING OFFICE i969 O-368-334, &

2. The combination of surface-active compounds of claim 1 whereincomponents (a) are present in an amount of from 75 to 35 percent byweight and components (b) are present in an amount of from 25 to 65percent by weight.
 3. The combination of surface-active compounds ofclaim 1 wherein R1 and R2 are different and one of R1 and R2 containsnot more than twice as many carbon atoms as the other of R1 and R2. 4.The combination of surface-active compounds of claim 3 wherein one of R1and R2 contains not more than 1.5 times as many carbon atoms as theother of R1 and R2.
 5. The combination of surface-active compounds ofclaim 1 wherein the sum of the carbon atoms in R1 and R2 is between 14and
 20. 6. The combination of surface-active compounds of claim 1wherein at least 50 percent of said mixture of anionic surface-activecompounds and non-ionic surface-active compounds of component (a) issaid anionic surface-active compounds selected from the group consistingof surface-active sulfonates, surface-active sulfates and straight-chainfatty acid soaps.
 7. The combination of surface-active compounds ofclaim 1 wherein at least part of said mixture of anionic surface-activecompounds and non-ionic surface-active compounds of component (a) issaid straight-chain fatty acid soap and the fatty acids present in saidsoap consist of at least 50 percent of saturated fatty acids with from16 to 30 carbon atoms, wherein foaming of said combination ofsurface-active compounds in water is reduced at higher temperatures. 8.The combination of surface-active compounds of claim 7 wherein at least3 percent of said fatty acids in said soap have from 20 to 30 carbonatoms.
 9. The combination of surface-active compounds of claim 7 whereinat least 5 percent of said fatty acids in said soap have from 20 to 30carbon atoms.
 10. The combination of surface-active compounds of claim 1wherein a further content of enzymes is present selected from the groupconsisting of proteases, amylases, lipases and mixtures thereof, whereinthe enzymatic activity is in the range of 62.5 to 50,000 LVE per gram ofthe combination of surface-active compounds in the case of proteases, of25 to 50,000 SKBE per gram of the combination of surface-activecompounds in the cases of amylases and of 2.5 to 10,000 IE per gram ofthe combination of surface-active compounds in the case of lipases. 11.Washing agents and washing agent adjuvants containing from 5 to 80percent by weight of the combination of surface-active compounds ofclaim 1 and from 20 to 95 percent by weight of a builder selected fromthe group consisting of neutral to alkaline reacting inorganic has beeninserted therefor.
 12. The washing agents and washing agent adjuvants ofclaim 11 containing from 15 to 40 percent by weight pf said combinationof surface-active compounds and from 85 to 60 percent by weight of saidbuilders.
 13. The washing agents and washing agent adjuvants of claim 12wherein at least 30 percent by weight of said builder is selected fromthe group consisting of condensed alkali metal phosphates and organicbuilders.
 14. Washing agents in powder to granular form containing acompatible textile softener consisting of (a) from 12 to 30 percent byweight of a combination of surface-active compounds consisting of (1) 25to 65 percent by weight of surface-active compounds selected from thegroup consisting of sulfonates and sulfates, (2) 5 to 40 percent byweight of non-ionic surface-active compounds, (3) 10 to 50 percent byweight of straight-chain fatty acid soap, (4) 25 to 65 percent by weightof a textile softener selected from the group consisting of (i)compounds of the formula wherein R1 and R2 are alkyl having from six to18 carbon atoms and n represents an integer from 0 to 2, and (ii)water-soluble salts thereof, (5) 0.5 to 5 percent by weight ofnon-surface-active foam inhibitors effective at temperatures of 60* Cselected from the group consisting of N-alkylated aminotriazines andaminotriazine adducts with propylene oxide and/or butylene oxidecontaining from 10 to 100 polyglycol units; (b) 40 to 85 percent byweight of builders, at least part of the builders being alkalinereacting, said builders weighing from 1 to 5 times that of component(a); and (c) 3 to 30 percent by weight of soil suspension agents. 15.The washing agents of claim 14 wherein a further content of enzymes ispresent selected from the group consisting of proteases, amylases,lipases and mixtures thereof wherein the enzymatic activity is in therange of 50 to 5,000 LVE per gram of total washing agent in the case ofproteases, of 20 to 5,000 SKBE per gram of total washing agent in thecase of amylases and of 2 to 1,000 IE per gram of total washing agent inthe case of lipases.
 16. The washing agents of claim 14 wherein saidnon-surface-active foam inhibitors of component (a) (5) is incorporatedwith solid particles of the washing agent with said foam inhibitorssurrounding at least partially said solid particles.
 17. Prewashingagents in powder to granular form containing a compatible textilesoftener consisting of (a) from 5 to 8 percent by weight of acombination of surface-active compounds consisting of (1) 25 to 65percent by weight of surface-active compounds selected from the groupconsisting of sulfonates and sulfates, (2) 5 to 40 percent by weight ofnon-ionic surface-active compounds (3) 10 to 50 percent by weight ofstraight-chain fatty acid soap, (4) 25 to 65 by weight of a textilesoftener selected from the group consisting of (i) compounds of theformula wherein R1 and R2 are alkyl having from six to 18 carbon atomsand (ii) water-soluble salts thereof, (5) 0.5 to 5 percent by weight ofnon-surface-active foam inhibitors effective at temperatures over 60* Cselected from the group consisting of N-alkylated aminotriazines andaminotriazine adducts with propylene oxide and/or butylene glycolcontaining from 10 to 100 polyglycol units and (b) from 95 to 92 percentof builders.
 18. The prewashing agents of claim 17 wherein a furthercontent of enzymes is present selected from the group consisting ofproteases, amylases, lipases and mixtures thereof wherein the enzymaticactivity is in the range of 50 to 5000 LVE per gram of total washingagent in the case of proteases, of 20 to 5,000 SKBE per gram of totalwashing agent in the case of amylases and of 2 to 1,000 IE per gram oftotal washing agent in the case of lipases.